High pressure alkylation reaction



Patented Aug. 10, 1 943 HIGH PRESSURE ALKYLATION REACTION Hans G. Vesterdal, Elizabeth, N. J., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing.

Application November 30, 1940, Serial No. 368,035

Claims. (01. 260-6834) This application is a continuation in part or an application, U. s. Serial No. 359,895, filed October 5, 1940.

The present invention relates to the alkylation and/or polymerization reactions in which parafiins both straight and-branched chain are condensed with olefins and/or oleflns are condensed with either similar or dissimilar olefin molecules to yield normally liquid, branched chain, satu rated and/or unsaturated hydrocarbons which find uses as blending agents and have direct application to utilization in the production oi motor iuels.

It is known to condense isoparaflins with olefins and/or to condense olefins with similar or dissimilar olefin molecules to produce alkylation reaction products and/or polymerization products. This has been done thermally, that is, by the application o'iheat alone, and it has also been accomplished by resorting to the use of certain catalysts under quite varying reaction conditions. Among the catalysts employed for eiIectlng condensation of olefins, either with themselves or with normal or isoparamns, may be mentioned concentrated sulfuric acid, aluminum chloride with or without the use of hydrogen halide, and various other Friedel-Crafts type catalysts, boron fluoride-water and boron fluo-= ride-hydrogen fluoride mixtures and theirresulting chemical compounds, phosphoric acid either alone or deposited on carriers such as kieselguhr and the like, and various other similar compounds.

The process of the present invention is primarily concerned with the production of normally liquid, branched chain, substantially completely saturated hydrocarbons boiling within the motor fuel boiling range, but is of necessity concerned with the production of polymers of olefins since the reaction taking place according to the process of the present invention is not one of alkylation to the exclusion of one '01 polymerization. In other words, while it is possible to produce substantial quantities of polymers in the reaction mixture, nevertheless it is an object of the present invention to so manipulate the reaction conditions, catalyst, reaetants, etc., to obtain as high yields as possible of the desired alkylates. The product as prepared according to the present invention therefore predominates in saturated, branched chain, normally liquid hydrocarbons.

, The process of the present invention may be in general described as eflecting a condensation between at least one parailin either straight or action with either water, hydrogen sulfide, or -mixtures of water and hydrogen sulfide, it is branched chain and at least one olefin, preierably a monooelfin, and/or a condensation between an olefin, preferably a monoolefln, and another olefin either of similar or dissimilar con.-

figuration, these two types of reaction being carried out simultaneously under reaction conditions conducive to the production oinormally liquid hydrocarbon condensation products, the said reactions being catalyzed by the presence of one or more substances taken from the group consisting of oxides and sulfides of metals of groups 5, 6 and '7 of the periodic system. In

,carrying out this process it is desirable, however,

in order to securethe desired results to have present in the reactionzone during thereaction small amounts of a substance having the formula 'I-IaX, wherein X is either oxygen or sulfur. In

other words, the reaction is carried out in the .presence oiwater or hydrogen sulfide. However,

it may also be carried out in the presence of a mixture of these two substances. Fundamentally,

the reaction is a vapor phase process. However, under certain restricted specific reaction conditions where a proper choice of reactants has been made it may be possible and at times desirable to carry out the reaction in the liquid phase.

Ordinarily, however, vapor phase reaction is prefact at times undesirable, to employ only one of these specific compounds alone as the catalyst. It is oftentimes desirable to employ a mixture of two or more 0! these catalysts. For example,

chromium and molybdenum oxides may be employed, vanadium and chromium oxides, vanadium and molybdenum oxides, or a three-component catalyst such as, for example, vanadium,

chromium and molybdenum oxides. It is within the scopeot the present invention to employ mixedlcatalyst of oxides and sulfides, for example, chromium oxide admixed with molybdenum sulfide. However, in promoting this rewellto keep in 'mind that under the usual reaction conditions ii sumcient amounts of hydrogen sulfide are present as the promoter eventually the oxide catalyst will-be converted into the corresponding sulfide compounds. In one embodiment of the invention the oxide catalysts may be preferred, not only because of their excellent activity with respect to alkylation but also because of their greater ease of regeneration; The regeneration process will be described hereinafter. Furthermore, there is one other advantage to the use of the oxide catalysts, particularly when used in connection with water as the promoter, and that is with respect to the recovery of the desired final products. In cases where sulfides and hydrogen sulfide are employed in the reaction, it is oftentimes necessary to resort to an alkali wash in order to remove from the final product dissolved sulfur compounds, whereas in connection with the use of oxide catalyst with a water promoter it is unnecessary to subject the final desired product to such purification treatment.

Although the above described catalysts may comprise the sole constituents of the catalyst compositions employed in the process of the invention, it is desirable particularly in commercial operations and from the economical standpoint to employ the active catalyst constituents in conjunction with a carrier. The types of carrier employedmay be quite varied in nature and although no determination has been made it is felt that in some instances the carriers are not inert in the reaction and in some manner contribute to the ultimate final yield of the desired products Carriers may be either-of the porous or non- Porous type, although since the reaction emasaasse about 10% or even as high as 30%, preferably between 7% and 20% by weight of the amount of carrier employed. Runs have been made employing catalysts wherein the metal oxides or sulfides constitute as high as /3 of the total weight of the catalyst. The optimum percentages'of metal oxides or sulfides deposited on the various carriers depends to some extent upon the available surface area of the carrier employed. Also, depending upon the reaction conditions, the amount of catalytic component of the catalyst mass'may vary considerably. Thus, when carryins out the reaction under drastic reaction conditions a lesser amount of the catalytic component milder reaction conditions, in which case a larger bodying the invention is thought'to beessentially a surface reaction it is preferred to employ the porous carriers. These carriers ar of the type such as clays, either natural or acid activated.

the gels such as, for example, alumina gel or silica gel, bauxite, fullers earth, bentonite, kleselguhr,

tion of said carriers, for example, silica gel or alumina gel, by admixing with the corresponding hydro gels salts of the various metals which upon thermal treatment decompose to give the desired oxides. The sulfides of the above-mentioned metals may be incorporated in the porous carriers by precipitating the aforementioned metal salts on the hydro gels and heating in the same manner as the oxides are produced. This catalyst mass may be then treated with hydrogen sulfide,

ammonium sulfide, or some equivalent sulfide compound in order to convert the metal oxides to their corresponding sulfides. Mixtures of two or more of the porous carriers may be employed as, for example, a mixed alumina-silica gel or an activated carbon admixed with an alumina or silica gel. In connection with the deposition of the metal oxides or sulfides on the non-porous type carriers, it is sometimes advantageous to em-'- Dloy a binder. Generally, however, a wetting of the nonporous carrier followed by dryin thermal treating to convert to the oxide is sum cient. to. leave a coating on the carrier which is adequate for use in the reaction. The amount of oxides and/or sulfides of the heretofore desi nated metals deposited may vary considerably with respect to the carriers employed. In general,

. however, the ultimate percentage of oxide and/or sulfide of the metals impregnated in or deposited on these carriers varies betweenabout 1% and portion of the catalyst mass is preferably the active catalytic component.

The catalyst may be prepared in any desired form such as, for example, pills, pellets, briquettes or powder, or some other finely divided or comminuted form. It-is likewise possible and at times preferred to ex'trude the catalyst composition,

particularly where the gels are employed, in the" form of the hydro gels through orifices of predetermined size. The extruded catalyst is then heated to drive off the water and to decompose the metal salts to the corresponding metal oxides or sulfides.

The specific oxides and sulfides employed in the process of the invention may vary in form depending upon the degree of oxidation of the particular metal. In general, it is proposed to employ those oxides and sulfides of metals which constitute at least theoretically the acid anhydrides of those metals employed. Thus, for example, CraOa is employed since it is considered to be the acid anhydride of chromous acid. C103 is employed since it is considered to be the acid anhydride of chromic acid. Similarly, M003 is employed as being the counterpart of molybdic acid. This analogy likewise applies to the sulfides since.

for example, Moss is considered the acid anhy Vast, Vase, V282, V205, V204, V203 and V202. The

manganese compounds include MnSz, MnS, Munoz, MmO'I, M11102, etc. It should be distinctly understood, however, that although no definite information is to be had at the present time. these various oxides and sulfides when desposited on the carriers and employed in the reaction under the hereinafter specified reaction conditions are very probably altered to a more or less extentin their chemical structure by reason of the reaction conditions.

A catalyst of the type employed may be prepared by co-precipitating the hydroxides of aluminum and chromium wherein the molar ratio of aluminum to chromium is ultimately to be about 2:1 with ammonia from a solution of the aluminum and chromium nitrates. The resultant gel is washed and dried, molded or pressed into the desired shape, for example, pills, and then heated to about 800 F. for a length of time sufilcient to substantially completely dehydrate the same. To

' process.

= of molybdic oxide in the final product. The resultant mass was washed and heated for about 30 minutes at 1200 F. The powder obtained was then pressed or briquetted into the desired pellet form for use in the reaction. Another catalyst which has found use in the present reaction was prepared by as aluminum hydroinde with silica hydro gel and adding thereto a suilicient amount of an aqueous solution of ammonium vanadate and homogenizing the same. The resultant mass was then washed, freed of excess water, pilled and then heated to about 800 F. for about 3 hours. This composition contained about 1.7% of vanadium pentoxide. of silica to alumina was maintained at about The reaction may be carried out using a variety of reactants. v the constituents of the feed stock be an acyclic paramn, that isran open chain parac hydrocarbon containing primary, secondary or tertiary carbon atoms-in the molecule.

Such compounds It is desirable that at least one of The weight ratio 3 flnery stabilizer bottoms, from stabilizer overhead gases, etc. In general, it is preferred to employ a molar excess of the paraflinic components of the feed stock with respect to the total oleflnic content of that feed stock. A molar ratio'of parafiins to olefins of at least 2:1 and preferably of at least 5:1 is desirable. Molar ratios running as high as 30:1 are, however, within the scope of the present invention, although it is to be understood that equal molar ratios may beemployed without attendant sacrifice in quality of the product in some instances.

The process may be carried out either as a batch, continuous or semi-continuous type of operation. -Economic considerations make it preferable to carry the process out in a continuous manner, especially where the process is operated on a commercial scale. The reaction as ethane, propane, n-butane, isobutane. isopentane, n-pentane, sec-pentane and higher homologues are suitable as one of the reactants in the Mixtures of two or more of th paraifins may likewise be employed, particularly where safety fuels and aviation naphthas and the like are the desired final products. The

presence of normal paramns in admixture catalyst since the reaction is apparently a. contact type and higher yields of the desired product are obtained by a vigorous and intimate mixing or agitation ofthe reactants in the presence of and in contact with the catalyst mass under the reaction conditions. In general, however, under the reaction conditions this degree of agitation is attained without the use of any external or mechanical mean of agitation being employed. No particular type of apparatus is required to successfully carry out the reaction. Equipment customarily employed for the catalytic dehydrogenation of parafilnic hydrocarbons under supermaintained may vary considerably. The reaction reaction to form the corresponding oleflnic compounds. Not only are the corresponding olefinic compounds thought to be formed but likewise to some extent at least it is thought that the paraflins either of the branched or straight chain type undergoing dehydrogenation may be isomerized to the corresponding straight or branched chain type. as the case'might be.

The-olefinic reactants may be selected from,

a number of the common olefins present in refinery gases and to be found elsewhere as well.

For example, ethylene, propylene, normal butylenes, isobutylene, the isomeric pentenes, and similar higher monoolefinic hydrocarbons of either a straight chain or branched chain character, may be employed. Mixtures of two or more of these olefins may be employed as the oleflnic components of the feed stock. It is generally preferred to employ normally gaseous oleflns as the reactants but this ischiei'ly because of economic factors.

polymers, copolymers, interpolymers, etc., of the above-mentioned monooleflns, these being, for' paraflins are to be found in the gases coming from the thermal and/or catalytic-cracking units of an'oil refinery, from-field butanes which may have been subjected to prior isomerization and/ or partial dehydrogenation treatments, from re- N'ormally liquid monooleflns.' however, are equally utilizable; Such olefins are is carried out under, temperatures ranging between about 375 F, and about 950 1'2, preferably between about 575 F. and about 800 F. It is realized of course that with each particular type of catalyst employed the optimum temperature 7 varies considerably but in general the above temperature ranges are adequate for carrying out the reaction to give the desired motor 'fuel products. 7

The process is carried out under fairly high superatmospherio pressures. Pressures ranging between about 500 and about 16,000 pounds per square inch, preferably between about 1500 and about 14,000 pounds per square inch, are employed. The time of contact of the reactants with the catalyst under the temperature and pressure conditions above mentioned may vary considerably depending upon the temperature, pressure and nature of the reactants employed. In general, the time of contact lies between about 1 and about 60 minutes, preferably between about 10 and about 30' minutes. Reasonable care should be exercised in correlating the abovedeflned reaction conditions together with the type of feed stock employed so as to avoid substantial cracking or carbonization of the hydrocarbons ted to the reaction zone. Obviously, a

' temperatureas high as 950F. with a pressure of around 500 pounds per, square inch and a conditions should be sufllciently drastic to eil'ect a substantial condensation of the oleflnic components of the feed stock principally with the paraflinic components of that feed stock or at Likewise, the

least with another portion of the same or different oleflnic components of that feed stock. In other words, an extremely mild condition when employing diisobutylene with Ca and Cr parafilns, that is, a contact time of around 1 minute when using a pressure of around 500 pounds per square inch and a temperature of around 375 F. would obviously not be sufflcient to produce the desired result. Suifice it to say that the optimum reaction conditions for any particular feed stock to give the desired final products are best deter mined for any particular catalyst employed by one or two trial runs at varied temperatures,

. pressures and times of contact within the ranges heretofore outlined and in accordance with the principles of the invention as heretofore stated.

The amount of hydrogen sulfide and/or water added to the reactants or conducted directly into the reaction zone varies to a certain extent depending upon the amount of active catalyst present in the catalyst composition. In general, the amount of promoter added to the reaction or present in the reaction zone at any one time should be between about 0.5% and about 20% by weight of the catalyst mass, preferably between about 5% and about 15% by weight. As will be understood from the hereinafter described runs under the particular reaction. conditions therein outlined, about by weight of water was found to be optimum therein. As a general guide in determining the amount of hydrogen sulfide or water to be present in the reactor at any one time, it may be stated that suificient promoter should be present in contact with the catalyst to at least afford a monomolecular film of the promoter in contact with the active surface of the catalyst mass.

After prolonged usage of the catalyst mass in the present reaction, in some cases after usages amounting to as long as 4,000 hours, the catalytic activity becomes somewhat impaired. The addition of elemental oxygen or elemental sulfur, depending upon whether the catalyst employed is an oxide or a sulfide, will to some extent reactivate the catalyst. The inactivity ofthe catalyst after prolonged usage has: been thought to be due largely to an accumulation or building up and clogging of the pores of the catalyst'or covering of the catalyst surface with carbonaceous deposits. The introduction of oxygen or sulfur, particularly where the carbonaceous deposits are of a soft or gummy consistency, will in some cases purge the mass of these deposits, and although not completely reactivating the mass, will substantially revivify the same and fit it for further usage in the reaction. In order to completely reactivate the catalyst once its catalytic activity has become substantially impaired, the catalyst is withdrawn from the reaction and, in the case of the oxide catalysts, the original activity may be restored by the introduction of air or oxygen either diluted with inert gases such as, for example, nitrogen or carbon dioxide or steam, at temperatures of between about 800 F. and about 1300' F. for a sufficient length of time to enable the rapid oxidation of the carbonaceous material to substantially completely remove the same from the pores and from the surface of the catalyst mass. This introduction of free oxygen-containing materials should be controlled so that the regeneration follows a fairly even course and avoids the burning of! of the carbonaceous mass at erratic rates since the heat 'of combustion is diflicult to remove where the oxidation process becomes too rapid. After the methods for regenerating catalysts employed in hydrocarbon reactions and the process of the invention is by no means limited or restricted to the described regenerative method. Any suitable regenerative method may be employed.

The regeneration or reactivation of the sulfide catalysts may require a somewhat different type of treatment. The above-described process for regeneration of the oxide catalysts may be resorted to and the resultant reactivated catalyst mass which finds the metal in combination with oxygen rather than sulfur is then dissolved in ammonium hydro sulfide and treated with hydrogen sulfide to form the ammonium thio metallate. Acidification of this mass with sulfuric acid precipitates the metal sulfide which is then heated in the presence of a reducing gas such as, for example, free hydrogen, at between about 500 F. and about 800 F. to form the more stable and more active metal sulfide catalyst. This material may then be formed into pills and the like or it may be directly reused in the proces of my invention.

As illustrative of the method of carrying out the process of the invention, but without unduly restricting the invention to the scope specifically disclosed, the following examples are submitted:

Example 1 A high pressure bomb capable of withstanding pressures up to 15,000 pounds per square inch at 1100 F. was charged with about 90 grams of a ture of the bomb was about 735 F. and the final pressure was about 11,000 pounds per square inch, the pressure at the end of the propylene addition having been about 14,000 pounds per square inch. The reacted mixture was removed .from the bomband the normally liquid product constituting the 05+ fraction was isolated and constituted a yield of about 160% based on the total propylene reacted .and a yield of about based on the total propylene charged to the reactor. This product amounted to about 107.5 grams and the product corresponding to the C5-C8 fraction amounted to about 54% of the total normally liquid product and had a bromine number of about 39. The residue amounting to about 46% of the product recovered had a bromine number of about 30. An increase in the Cs-Ca component of the product could be obtained in this run if the olefin had been added more slowly and a higher molar ratio of isobutane to propylene had been maintained in the reaction zone. The isobutane to propylene molar ratio actually amounted to about 3:1 as the run was carried out.

Under comparable conditions except that no water was added to the catalyst mass prior to the about 34.

reaction, the yield of normally liquid product amounted to about 50% based upon the olefin charged, or about 89% based upon the olefin consumed. The CsCe fraction in this particular run was about 44% of the normally liquid product recovered and it had a bromine numberw of about 69. a

Under comparable conditions, except that no catalyst was employed and no water was added. the product obtained amounted to about 43% or the olefin charged or about 86%oi the olefin reacted, and the Cs-Ga cut constituted 12.5% of the product and had a bromine number of about 17. In view or the fact that the run madewithout the catalyst and without the addition of water gave a C5-C8 out having a bromine number of 17, in contrast to a bromine number for the same cut of about 39 when employing water and the catalyst, it would appear that to some extent at least a dehydrogenation reaction had occurred when the catalyst and water were employed in the reaction. Likewise, where the water was absent but a catalyst was employed, the bromine number of the Cs-Ca cut was higher than when the water was employed. In that case the bromine number was 69, whereas in the case where water was employed the bromine number was about 39.

The use of only 5% water under comparable conditions gave substantially the same yield of normally liquid product as when water was absent. However, the Ce-Cs out in the normally 1 and 2 was charged with about the same amount of a catalyst prepared by co-precipitating aluminum hydroxide and chromium hydroxide with 393 grams of isobutane. While maintaining the pressure at about 7,400 pounds per square inch liquid product was 53.8%, and the bromine numher was about 61. When using about 20% of water, the other reaction conditions being comparable to those specified in Example 1, the yield oi normally liquid product constituted about 48% of the propylene charged to the bomb or about 141% based upon the propylene consumed and the C&Cs fraction amounted to about 55.5% of the normally liquid product and this fraction had a bromine number of about 49.

7 Example 2 g i A bomb of thesame type as specified in Example 1 was. charged with the same catlyst emgrams of isobutane were charged to the reactor under a pressure or about 7,000 pounds per square 1 inch. About 101 grams of propylene were slowly added over a period or 16 minutes to the catalyst and isobutane mixture andthe pressure rose from about 7,000 pounds per square inch to about 12,400 pounds per square inch andlthe temperature remained substantally the same. The bomb was shaken and the heating was continued ror an additional 30 minutes, at the end or which time the pressure had dropped to about- -9,000 pounds per square inch with the temperature being maintained at around 770 F. normally liquid product amounted to about 87.4 arenas and this amounted to a yield of about 87% based on the propylene charged or about 185% there was added about 116 grams of propylene gradually over a. period of about 18 minutes, during which time the pressure rose to about 12,800 pounds per square inch. The bomb was shaken and the heating continued for an additional 30 minutes. The final temperature of the bomb was about 770 F. and the final pressure was about 9,000 pounds per square inch. Thenormallyliq uid product recovered from the reaction mixture amounted to about 118 grams which constituted a yield of about 101.5% based on the propylene charged or a yield of about 144% based on the propylene consumed. The Ce-Ca cut obtained from this product amounted to about 57.3% and had a bromine number of about 25. The residue had a bromine number of about 29.

Under comparable conditions, except that the.

temperature was maintained at around 700 F. but no water as a promoter was employed in conjunction with the catalyst, .the normally liquid product obtained amountm to about 36% based upon the propylene charged or about 92% based on the propylene consumed. The Cs-Ce fraction which amounted to about 41.2% of the recovered product had a bromine number or about 51.

Example 4 or V204. The homogenized mixture was dried, pilled and then heated to about 800 F. for about 3 hours. The -weight ratio or-silica to alumina was about 1.7 to 1. To this catalyst there was added about 11% by weight or" water and ad: mixed with this catalyst mass was 365 grams of isobutane. To this reaction mixture there was slowly added over a period of about 19 minutes,

The.-

besed on the propylene consumed. The Cs-Cl Example 3 A bomb similar to that employed in Examples stituted the 05-00 fractions It had a bromine while maintaining the reaction mass at a temperature of between about 700 F. and about 720 F., about 115.8 grams of propylene. The pressure rose from an initial pressure of about 7,000

pounds per square inch to around 14,000 pounds per square inch. The bomb was shaken and the reaction mixture was maintained under these' reaction conditions for an additional 30 minutes,'

at the end of which time the temperature was around 720 F. and the pressure was about 13,000 pounds per square inch. A normally liquid prodnot was recovered in an amount or about 100.7 grams which amounted to about 87.2% or the propylene charged or about 115.4% or the propylene reacted. or this product about 55.8% connumber of 54, while the residue had a bromine number of about 19.

Eztample In a high pressure bomb capable of withstanding pressures up to about 15,000 pounds per square inch at 1100 F. there was charged about 90 grams of a catalyst composed of molybdenum oxide impregnated on alumina gel in which the amount of molybdenum oxide was about 9%. To this catalyst there was added sumcient water to constitute about 11% by weight of the catalyst. While maintaining the .bomb and its contents at a temperature of about 800 F. there was charged about 341 grams of propane and over a period of about 20 minutes there was added gradually about 151 grams of isobutylene. The bomb was shaken and heated for an additional 40 minutes. The final temperature of the bomb was about 800 F. and the final pressure about 9,400 pounds per square inch, the pressure at the end oi! the isobutylene addition being about 10,900 pounds per square inch. The mixture was removed from the bomb and the normally liquid product constituting a Cs+ fraction was isolated and was obtained in a yield of about 105% based on the total isobutylene reacted and ayield of about 94.6% based on the total isobutylene charged. The product amounted to about 131 grams and corresponded roughly to a C5-Cs fraction in an amount oi about 65% of the total product, about one half of which was 01 and had a bromine number between 12 and 18. The residue amounted to about 35% of the product recovered and had a bromine number of about 36. The propane: isobutylene molar ratio maintained in the reaction was about 2.86: 1.

Example 6 Using the same type of bomb for carrying out the reaction and the same amount of a catalyst about '69 grams oi propylene gradually over a period of about 12 minutes during which time the pressure rose to about 8,000 pounds per square inch. The bomb was, shaken and the heating continued for an additional 108 minutes.

v.The final temperature of the bomb was about 800 1". and the final pressure was about 7,600 pounds per square inch. The normally liquid product recovered amounted to about 82.5 grams,

whichwas prepared as defined in Example 3,

which constituted a yield of about 121% based on The residue boiling above 180 F. constituted 51.8% o! the product with a bromine number of 31- and D20a=1.4250. From this it can readily asaaeec can be seen that the Co out had an approximate percentage of saturation of 89. Furthermore, by reason of the refractive index 01' 1.3750, it is readily seen that this fraction comprised almost pure 2,3-dimethyl butane.

Example 7 Another run was carried out employing the same catalyst as in the preceding run and the same amount of water. The bomb was maintained at a temperature of about 750 F. and

originally contained about 343 grams of normal butane. The pressure was maintained at about 5,200 pounds per square inch and there was gradually added about 163 grams of isobutylene over a period of 20 minutes. The pressure then rose to about 11,500 pounds per square inch. The bomb was shaken and heated for an additional 40 min utes, at the end of which time the pressure had dropped to about 10,000 pounds per square inch and the final temperature was about 765 F. The normallyliquid product constituting (15+ was recovered in a yield of about 160.2 grams, which constituted a yield of about 98.4% based on the isobutylene charged, and a yield of about 118.5% based on the isobutylene reacted. A cut was recovered having a boiling range from 55 F. to 310 F. (C5Ca) in an amount constituting about 69.2% of the product-recovered and it had a bro- .mine number of about 28. The residue, which constituted 30.8% of the product, had a bromine number of about 34.

The nature and objects of the invention having been thus fully described and illustrated, what is claimed as new and useful and desired to be secured by Letters Patent is:

I 1. A process of reacting paraiilns with olefins to produce saturated, normally liquid, branched chain hydrocarbons which comprises carrying out said reaction at temperatures between about 375 F. and about 950 F. under superatmospheric pressures in contact with a catalyst mass whose essential components are selected irom the group consisting of oxides and sulfides of metals of groups 5 and 6 or the periodic system, and in the presence or a small amount of at least one compound having the iormula nix, wherein X is a member or the group consisting of oxygen and 16,000 pounds per square inch for between about $6 and about minutes while correlating the reaction conditions to avoid substantial cracking and carbonization, in contact with a catalyst mass whose essential components are taken from the group consisting of oxides and sulfides oi metals 01 groups 5 and 6 oi! the periodic system, and in the presence or between about %%.and about 20% of the catalyst weight 01a compound nix, wherein X is a member of the group consisting of oxygen and suliur.

4. A process as in claim 3 wherein theparafiin is present in molar excess over the olefin and the catalyst is molybdenum oxide on alumina.

5. Aprocessasinclaim3whereintheparafiin is present in molar excess over the olefin and the catalyst is a chromium oxide on alumina.

6.Aprocessasinclaim3whereintheparamn is present in molar excess over the olefin and the catalyst is a vanadium oxide on a silica-alumina gel.

7. A process which comprises condensing normal butane with at least one normally gaseous olefin at a temperature between about 550F. and

"about 900 F. under a superatmospheric pressure between about 1000 and about 14,000 pounds per square inch iorbetween about and about 30 minutes in contact with a catalyst mass whose essential components are selected from the group consisting of oxides and sufides of metals of groups 5 and 6 of the periodic system and in contact with between about 5% and about by weight of the catalyst mass of a member of the group consisting of hydrogen sulfide and water, correlating the reaction conditions to avoid substantial crackingand carbonization and recovering normally liquid, branched chain, substantially saturated hydrocarbons from the reacted mixture.

*8. A process as in claim '1 wherein the catalyst is supported on and employed in conjunction with a carrier. a

9. A process for the production of a saturated,

normally liquid, branched chain hydrocarbon.

mixture containing substantial amounts of 2,3-ditemperatures and pressures in the presence of acatalyst mass whose essential components are selected from the group consisting of oxides and sulfides of metals of groups 5 and 6 of the periodic system while in the presence of a small amount of a compound having the formula HzX, wherein X is a member taken from, the group consisting of oxygen and sulfur. a

12. A process as in claim 11 wherein the paraihns comprise essentially normal paraflins. .13. A process which comprises condensing propane with'at least one normally gaseous olefin at a temperature between'about 550 F. and about 900 F. under a superatmospheric' pressure'between about 1000 and about 14,000 lbs. per square inch for between about 10' and about 30 minutes in contact with a catalyst mass whose essential components are selected from the group consisting of oxides and sulfides of metalsof group 6 of methyl butane which comprises condensing propane with propylene at a temperature of between about 180 F. and about 800 F. under a pressure between about 7,000 andabout 8,000 pounds per square inch for about 2 hours, the propane being in substantial molar excess or the propylene, in

contact with a chromium oxide impregnated in alumina gel, said catalyst-having added thereto correlating the reaction conditions to avoid substantial cracking and carbonization, in contact with a catalyst mass whose essential components are taken irom the group consisting of oxides and sulfides of metals of groups 5 and 6 or the periodic, system and in the presence 0! between about /z% and about 20% o! the catalyst weight of a compound fiaxwherein-x is a member of the group consisting oi omgen and sulfur.

- 11. A process which comprises-condensing p'araflins with moncoleflns under superatmospherio the periodicsystem and in contact with between about and about 20%, or the catalyst weight of a compound selected from the group consisting oi, hydrogen sulfide and water, correlating the reaction conditions to avoid" substantial cracking and carboniz'ation and recovering normally liquid, branched chain, substantially satu- I rated paraflins from the reacted mixture.

14. A process for the production of a saturated, normally liquid, branched chainv hydrocarbon mixture which comprises condensing propane I with isobutylene ata temperature of about 800 j F. under a pressure of between (about 9400 and about 10,900 lbs. per square inch for about 1 hour, the propane being in substantial molar excess of the isobutylene, in'contact with a molybdenum oxide impregnated on alumina gel catalyst mass, said reaction being carried'out in the presence of about 11% byweight of the catalyst or water, and recovering t e desiredhydrocarbone from the reacted mixt e. p

15. A' process for the production of a saturated,

' normally liquid, branched chain hydrocarbon mixture which comprises condensing normal' butanewith isobutylene at a temperature or about 750 F. and a pressure of between about 5200' and about 11,500 lbs per square inch for about 1 hour, the normal butane being present in substantial molar excess over the isobutylene, in the presence ofacatalyst mass comprising essentially molybdenum oxide impregnated on alumina gel, the reaction being carried out in the presence of about 11%01 water measured as liquid, and recovering the desired hydrocarbons from the -EANS G.

reacted mixture.- 

